Methine dyestuffs



Patented Apr. 20, 1948 i METHINE DYESTUFFS Oskar Itiester, Dessau, and Gustav Wilmanns, Wolfen, Kreis Bitterfeld, Germany, assignors, by mesne assignments, to General Aniline & Film Corporation, Neva-York, N. Y., a corporation of Delaware No Drawing. Application November 13, 1939, Se-

il'igasl8 No. 304,173. In Germany November 9,

' g 7 Claims. (Ql. 260--240) This invention relates to the production of methine dyestuffs.

According to the U. S. patent application Ser. No. 237,474, filed October 28, 1938, dyestuffs of R1 stands for alkyl or aralkyl,

R2 stands for alky1,-aralkyl, aryl,

X is an acid radical, for instance halogen,

.RrS04-, toluene-sulfalkyl, C104, etc.

the following constitution n is a number 0, 1 or 2.

Y The intermediat roduct: b/ e p R2 o= oHoH .=o 0- N 7C\ 0:5 C--CH=C (g- X" I! A N '1 1'3 C=(OH=CH)"=(1) o=s I f f o=c are obtained by reacting dyes which contain the I f rhodanine nucleus with alkylhalides, dialkylsul- R fates, etc., and further condensing the reaction products with nitrogen containing heterocyclic with alldehydes of the general formula. compounds which possess a reactive methylor Y methylene-group. v

It is an object of the present invention to provide a process for theproduction of similarly con- B stituted dyestuffs having improved properties.

A further object of the invention is the provi- I sion of new methine dyestuffs suitable as photo- R graphic sensitizers. or with intermediate products of the general for- Still further objects of the invention will be-- l come apparent from the detailed description following hereinafter.

We have found, that unexpectedly dyestuffs of similar constitution as the above mentioned dyestuffs can be obtained .by employing as starting. t materials dyes containing the thiohydantoine nucleus instead of the rhodanine nucleus pro- R X Dyestuffs of this constitution are of great inposed previously. The dyes are obtained according to the following formula: tensity and are especially useful for the sensitiz- R2 Y i 1 is obtained by condensing the thiohydantoine ing of silver halide emulsions especially for those emulsions commonly-used in color photography which contain. dyestuffs components fast to dif-. fusion. The dyestufis are not affected adversely in their sensitizing action by the color-forming A and B stand for the atom groupings necessary for completing the ring, such as for instance phenylene, naphthylene, etc.

Ystands for O, S, Se, development components in the emulsion.

alkyl\ /alkyl 7 Example 1 By condensingeven parts of methyl-allyl-thio- -CH#H, N-alkyl, N-aralkyl or N-aryl, hydantoine and 5.6-dimethyl-1-ethyl-2-w-phenylacetyl-amidopropene-benzthiazolium toluenesulfethylate of the following constitition HaC CHnCsHrSOT in 5-times their weight of pyridine for 4 hours at 110 C., the following intermediate product is obtained CsH5 This product is heated with dimethylsulfate at 110 C. The resultant addition product s CH3 HaG C=CH-CH=C 1130 :0 C-S-CH: OHaSOr' N CsHs I is converted into a dye by heating for two hours at 110 C., in pyridine with 5.6-dimethyl-2-methylbenzthiazolethyliodide. The dyestuff is precipitated by means of a solution of potassiumare reacted in 5. times their weightof pyridine to yield'a blue intermediate product of the following constitution:

This latter is heated with the same amount of dimethyl sulfate for minutes at 110 C. The resulting addition product is rubbed for a short while with absoluteether, the ether decanted and the addition product condensed for 2 hours at 110C. with an equal amount of Z-methylbenzoxazol-diethylsulfate. The dye isprecipitated'as w-aldehyde (produced according to the method described in U. S. patent application Ser. No. 248,230, filed December 29, 1938) and methylphenylthiohydantoine are dissolved in 5: times their weight ofpyridine and condensed by adding iodide. Its constitution is as follows: the same; amount of piperidine and heating for CH2 V S I 1130- /N\ S\ CH o=oH-oH=o mo 0 |3 oon=o I CH3 N l CaHs I I CaHu 02H. Absorption maximum ca 600 m 2 hoursvto 90 C. to yield an intermediateproduct Sensitization maXImum ca 630 m of the following constitution:

Example 2 S I (3113 The intermediate product named under- 1 is H condensed for 10 minutes at 110 C. with dimeth- O=CHCH=C ylsulfate and reacted for 3 hours at 105 C. in H16 0:8 5 times its weight of pyridine with even partsof N 2-methyl-benzselenazo1-diethyl-sulfate. A violet (32m dye of the following constitution results Even parts of dimethyl-thiohydantoine and 4- (w phenylacetyl amidopropene) 1 methyllepidinium-methylsulfate of the following constitution:

OOOHa l The yellow dye is converted into a compound of the following constitution:

by heating for 10 minutes with the same amount of dimethylsulfate at 100 C. This intermediate product is dissolved in. pyridine and condensed with the same amount of 2-methyl-4.5-naphthothiazoldiethylsulfate in pyridine to yield a redviolet dye of the following constitution:

Example 5 CH; CH2

1 gram of this product is heated with 1 cc. dimethylsulfate for half an hour at 90 C. and dissolved after washing with absolute ether in cc. of pyridine and then condensed to a violet dye of the following constitution:

I N CH3 l V with 2 grams of 2.5.6-trimethylbenzselenazoldiethylsulfate for 2 hours at 110 1 1 V Etrampl 6 231 mg. of the aldehyde in U. S. Patent No. 2,152,615) by splitting the polymethine dye and 144 mg. of dimethylthlohydantoine (obtainable from aminoacetic acid and methyl mustard oil) are heated in 1 cc. pyridine and 0.5 cc. acetic acid anhydride. After cooling the dye of the following formula precipitates:

1 gram of this dye (produced in several small batches) is heated with 1 cc. of dimethylsulfate for an hour at C. The oily product is rubbed with 10 cc. of ether. A viscous mass soluble in methanol with violet-red color results. Now, there is added 1 gram of 2-methylbenzthiazolethylsulfethylate and 3 cc. pyridine and the mixture is heated for an hour at C. To the intensely violet liquid there are added a few cubic centimeters of methanol and 2 cc. of an aqueous potassium iodide solution of 10 per cent strength.

A dyestuif of the following formula precipitates:

' o--oH=c'i CIHfi N G Ha 62H Absorption maximum in methanol 690 my sensitizing maximum 720 m ('I'he sensitizing maximum was determined by bathing an emulsion of medium sensitivity in a solution of the dye of 1 in 500,000.)

We claim:

1. A dyestuff having the following general formula A and B stand for an atom grouping capable of completing an organic ring system,

Y'stands for the member of the group consisting of O, 8, Se,

alkyl alkyl and -CH=OH-- R1 is 7 R2 is a member selected from the class consisting of alkyl, aryl'and X is an anion, and 'n, is a whole number smaller than 3.

2. A dyestufi' having the following general formula:

R and R3 represent a radical selected from the class consisting of c and m-N R1 is an alkyl,

R2 is a member selected from the class consisting of alkyl and aryl,

D represents the non-metallic atoms necessary to complete a, heterocyclic nucleus selected from the group consisting of five-membered and sixmembered heterocyclic nuclei,

E represents a radical selected from the group consisting of vinylene and phenylene groups,

X is an anion, and

n is a whole number less than 3.

3. A dyestuff having the following structural formula:

Isl-N I CaH Calls .1

4. A dyestuff having the following structural formula:

5. A process forthe production of'dyes comprising treating with an alkyl salta compound of the following general formula: I g 1 R: Y t A o= on-cn fl=o 0:0 T l N R l R2 wherein A and B stand for an atom grouping capable of completing an organic ring system, Y stands for a member of the group consisting of 0, S, Se, -CH=CI-I and alkyl C-- alkyl,

8 R1 is alkyl,

R2 is a member'selected from the class consistin of alkyl and aryl, and n is a whole number smaller than 3,

and condensing the intermediate so formed, in the presence of an acid binding agent, with a compound selected from the class of heterocyclic nitrogen compounds which have a nucleus of the type contained in cyanine dyes and which contain a reactive methyl group in the or. position to the ring nitrogen atom.

6. A dye intermediate of the following general formula:

A and B stand for an atom grouping capable of completing an organic ring system,

Y stands for the member of the group consisting of O, S, Se, -CH=CH and alkyl -C-- alkyl,

R1 is alkyl,

R2 is a member selected from the class, consisting of alkyl and aryl,

R3 is alkyl,

X is an anion, and

n is a Whole number smaller than 3.

7. A process for the production of dyes comprising treating with an alkyl salt a compound of the following general formula:

A and B stand for an atom grouping capable of completing an organic ring system, Y stands for a member of the group consisting of O, S, Se, CH=CH and alkyl --C-- alkyl, R1 is alkyl, R2 is a member selected from theclass' consistingof alkyl and aryl, and n is a whole number smaller than 3.

OSKAR RIES'I'ER. GUSTAV WILMANNS;

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,170,803 Brooker Aug. 29, 1939 2,177,408 Brooker Oct. 24, 1939 FOREIGN PATENTS Number Country Date France 1938 

